Plastisol composition, gelled film and article

ABSTRACT

A plastisol composition of the present invention comprises a polyalkylene glycol and/or a polyalkylene glycol derivative (X) and polymer particles (Y). This composition uses non-halogen based polymer particles with no halogen atoms, which do not emit materials such as hydrogen chloride gas or dioxin on incineration, and does not require a phthalic acid based plasticizer as a dispersion medium, and consequently provides an extremely large reduction in environmental impact. Furthermore, by using the plastisol composition, a gelled film having no bleed out of the dispersion medium, superior dispersion medium retention characteristics, workability, and processability is obtained. In addition, by using the plastisol composition of the present invention, a gelled film or an article with excellent mechanical characteristics are provided. The composition of the present invention is suitably used as materials such as wallpaper, floorings, vehicle undercoats, and vehicle body sealers.

TECHNICAL FIELD

[0001] The present invention relates to a plastisol composition using apolyalkylene glycol and/or a polyalkylene glycol derivative as adispersion medium, a gelled film and an article.

BACKGROUND ART

[0002] Vinyl chloride based sols comprising a vinyl chloride based resindispersed in a phthalic acid based plasticizer such as dioctyl phthalate(DOP) provide excellent workability and superior physical properties ofthe product film, and are consequently widely used in many industrialfields.

[0003] However, in recent years, with greater attention being paid toenvironmental issues, problems have arisen with vinyl chloride basedsols due to toxic materials derived from vinyl chloride based resins,such as the generation of hydrogen chloride gas on incineration and theresulting damage to incinerators, acid rain, and the generation ofdioxin during incineration.

[0004] Accordingly, plastisols using alternative resins to vinylchloride based resins are being actively investigated.

[0005] Moreover, environmental issues have also been identified for manygeneral purpose plasticizers such as the phthalate ester basedplasticizers which are used in vinyl chloride based plastisols.

[0006] Based on this background, Japanese Unexamined Patent Application,First Publication No. Hei 7-53934 and Japanese Unexamined PatentApplication, First Publication No. Hei 7-233299 propose acrylicplastisols using an acrylic based resin as an alternative to the vinylchloride based resin. By using an acrylic based resin instead of a vinylchloride based resin, these acrylic plastisols are novel proposals basedon environmental concerns, and offer superior performance from anenvironmental viewpoint as they do not generate hydrogen chloride gas ordioxin even when incinerated.

[0007] However, these acrylic plastisols use a phthalate ester basedplasticizer, and as such are unable to completely resolve all theenvironmental problems.

[0008] Japanese Unexamined Patent Application, First Publication No. Hei10-231409 discloses an acrylic based plastisol which uses a benzoateester based plasticizer as an example of an acrylic based plastisolwhich uses a plasticizer other than a phthalate ester based plasticizer.Furthermore, Japanese Unexamined Patent Application, First PublicationNo. Hei 8-100098 discloses an acrylic sol which uses a phosphate esterbased plasticizer. In addition, Japanese Unexamined Patent Application,First Publication No. 2000-281857 discloses an acrylic based plastisolusing a combination of an ether ester based plasticizer and a benzoateester plasticizer. According to these proposals, because a phthalateester based plasticizer is not used, environmental problems can beresolved.

[0009] However, the plasticizers disclosed in these patent applicationsdisplay inadequate compatibility with the acrylic resin, andconsequently, in gelled films formed with these types of acrylic basedplastisols, the plasticizer exists in a free state within the gelledfilm. As a result, if the gelled film is used for a long period, or usedunder particular conditions such as high temperature conditions, theplasticizer travels to and then bleeds out from the surface of thegelled film. When the plasticizer bleeds out from the gelled film, thegelled film becomes brittle, and the mechanical characteristics such asthe strength, the ductility, the flexibility, and the like tend todeteriorate. In addition, in cases in which ink or the like contacts thegelled film, the ink may transfer onto the gelled film.

DISCLOSURE OF INVENTION

[0010] An object of the present invention is to provide a plastisolcomposition with no environmental problems, wherein the dispersionmedium suffers almost no bleed out from a produced gelled film, and thegelled film has superior dispersion medium retention characteristics andsuperior mechanical characteristics.

[0011] As a result of intensive investigations, the inventors of thepresent invention found that polyalkylene glycols and/or polyalkyleneglycol derivatives differ from conventional plasticizers such asphthalate esters, and display low toxicity and have little impact on theenvironment, and are consequently extremely useful as plasticizers.Accordingly, they found that by using a polyalkylene glycol and/or apolyalkylene glycol derivative instead of a plasticizer as thedispersion medium within a plastisol, the problems described above couldbe solved, and were hence able to complete the present invention.

[0012] The main aspects of the present invention are a plastisolcomposition including a polyalkylene glycol and/or a polyalkylene glycolderivative (X) and polymer particles (Y), and a gelled film, and agelled film in which the quantity of bleed out of the dispersion mediumfrom the gelled film of 2 mm thick when the gelled film is retained for24 hours at 80° C. under a pressure of 200 Pa is no more than 1% of thetotal quantity of the dispersion medium.

BEST MODE FOR CARRYING OUT THE INVENTION

[0013] The present invention is explained by the following more detaileddescription.

Plastisol Composition

[0014] A plastisol composition of the present invention comprises apolyalkylene glycol and/or a polyalkylene glycol derivative (X)(hereafter referred to as a component (X)), and polymer particles (Y).

[0015] There are no particular restrictions on the polyalkylene glycoland/or polyalkylene glycol derivative used in the present invention, andknown compounds can be used. A polyalkylene glycol derivative refers toa compound with a structure in which either a portion, or all of thehydroxyl groups positioned at the terminals of the polyalkylene glycolhave been replaced with other functional groups.

[0016] Specific examples of the polyalkylene glycol includepolymethylene glycol, polyethylene glycol, polypropylene glycol,polybutylene glycol, polyhexamethylene glycol, polyalkylene glycols withat least two types of glycol unit such as copolymers of ethylene oxideand propylene oxide, and branched polyalkylene glycols usingpolyfunctional alcohols such as glycerine.

[0017] Specific examples of the polyalkylene glycol derivative includecompounds in which the terminals have been etherified such asmonoalkoxypolyalkylene glycols and dialkoxypolyalkylene glycols.

[0018] Of these, compounds represented by a general formula (1) shownbelow are preferred as the component (X) as they display excellentaffinity with acrylic polymer particles, and also display excellentdispersibility of acrylic polymer particles.

[0019] In the formula, R₁ and R₂ each represent, independently, ahydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R₃represents a straight chain or branched alkylene group having 2 to 12carbon atoms. Furthermore, n which represents the degree ofpolymerization of the polyether is an integer within a range from 5 to200, although the lower limit of the range is preferably an integer of10 or more. In addition, the upper limit of the range is preferably aninteger of 100 or less, and integers of 50 or less are even moredesirable. In cases in which n is less than 5, the molecular weight ofthe component (X) is small, and consequently during the heating processused for forming the gelled film, the volatile organic compounds (VOC)within the plastisol composition tend to be more prone tovolatilization. In contrast, if n is greater than 200, then theviscosity of the component (X) increases, and the handling of theproduct plastisol composition tends to deteriorate.

[0020] In addition, among the compounds represented by the generalformula (1), using either a single compound or a combination of two ormore compounds selected from among polyethylene glycols in which thenumber of carbon atoms of R₃ is 2, polypropylene glycols in which thenumber of carbon atoms of R₃ is 3, and polybutylene glycols in which thenumber of carbon atoms of R₃ is 4, is particularly preferred. Thereasons for this preference are that these polyalkylene glycols displayexcellent affinity with acrylic polymer particles and are consequentlyable to effectively plasticize the produced plastisol composition, andthat these polyalkylene glycols are produced industrially on a largescale and are consequently of low cost.

[0021] There are no particular restrictions on the structure of thepolymer particles (Y) used in the present invention provided theparticles are capable of being dispersed within the dispersion medium,and suitable examples include uniform structures, core/shell typestructures or gradient structures in which the composition varies in asubstantially continuous manner.

[0022] Of these, core/shell type structures and gradient structuresallow the internal composition of the polymer particles to be differentfrom the composition of the surface layer. Accordingly, by using astructure in which, for example, a polymer with good co-solubility withthe dispersion medium is provided within the internal sections of theparticles, the storage stability of the composition can be ensured, andwhen the composition is heated during film formation, the polymerpresent inside the core/shell structure or gradient structure, and thecomponent (X) undergo dissolution, enabling the dispersion medium to beretained within the gelled film. In this manner, core/shell structuresor gradient structures are preferred since they allow good storagestability of the plastisol and good dispersion and retention of thepolymer particles within the dispersion medium, and also produce gelledfilms with good physical properties.

[0023] The polymer particles (Y) can be produced by known polymerizationmethods, including emulsion polymerization in a water based medium, seedemulsion polymerization, soap-free polymerization, suspensionpolymerization, microsuspension polymerization, dispersionpolymerization in an organic medium, dispersion polymerization in awater/organic mixed medium, and precipitation polymerization in anorganic medium. Furthermore, the polymer particles (Y) can also beproduced by a combination of a plurality of these known polymerizationmethods.

[0024] In the present invention, in those cases in which polymerparticles (Y) with a core/shell structure are used, emulsionpolymerization, seed emulsion polymerization, and soap-freepolymerization are preferred from among the polymerization methodsdescribed above since they provide good control of the particlestructure and enable a high molecular weight polymer to be produced.Furthermore, microsuspension polymerization methods are also preferredsince the particle size distribution of the polymer particles is narrow,enabling polymer particles with a uniform particle size to be obtainedrelatively easily, and since a core/shell can be formed by a posttreatment such as alkali hydrolysis, following the polymerization.

[0025] The method of recovering a powder of the polymer particles (Y)from the polymer dispersion obtained using the polymerization methodsdescribed above can be any method which enables recovery of the polymerin a particle state, and suitable examples include spray drying methods,coagulation methods, freeze drying methods, centrifugation methods, andfiltering methods.

[0026] Of these, spray drying methods are preferred since they enableproduction of the polymer particles (Y) with good productivity, at lowcost, and with ready control of the form of the polymer particles, andbecause a plastisol composition comprising polymer particles (Y)obtained by spray drying is capable of forming a gelled film withsuperior mechanical characteristics.

[0027] There are no particular restrictions on the particle size of thepolymer particles (Y), and this size can be selected appropriately inaccordance with the desired performance of the product composition andthe gelled film that is formed.

[0028] For example, in those cases in which the viscosity of theplastisol composition is to be lowered, coating workability improved,the dispersion stability of the polymer particles within the dispersionmedium improved, the storage stability improved, and the film formingproperties of the plastisol composition also improved, the lower limitfor the volume average particle size of the primary particles of thepolymer particles (Y) is preferably 0.01 μm or greater, and even morepreferably 0.1 μm or greater, and most preferably 0.5 μm or greater.Furthermore, the upper limit is preferably 50.0 μm or less, and evenmore preferably 10.0 μm or less, and most preferably 2.0 μm or less.

[0029] If the volume average particle size of the primary particles ofthe polymer particles (Y) is less than 0.01 μm, then the viscosity ofthe product plastisol composition will increase, and the coatingworkability tends to deteriorate. Furthermore, the dissolution speed ofthe polymer particles (Y) increases, and the storage stability of theplastisol composition tends to deteriorate. On the other hand, if thevolume average particle size of the primary particles of the polymerparticles (Y) is greater than 50 μm, then, the fusion of the polymerparticles (Y) tends to worsen, when an applied coating of the plastisolcomposition is heated to form a gelled film.

[0030] There are no particular restrictions on the molecular weight ofthe polymer particles (Y) used in the present invention, and themolecular weight can be selected appropriately in accordance with thedesired performance of the product composition and the gelled film thatis formed.

[0031] For example, from the viewpoint of storage stability of thecomposition, the weight average molecular weight of the polymerparticles (Y) is preferably 100,000 or more, and even more preferably300,000 or more, and most preferably 500,000 or more. Furthermore, fromthe viewpoint of the film forming properties of the composition onheating, the molecular weight is preferably 5,000,000 or less, and evenmore preferably 2,000,000 or less, and most preferably 1,000,000 orless.

[0032] There are no particular restrictions on the structure of thepolymer particles (Y) used in the present invention. The structures maybe formed only from primary particles, or may be secondary structuresformed from secondary particles such as particles in which primaryparticles are cohered with weak cohesion, particles in which primaryparticles are cohered with strong cohesion, and particles in whichprimary particles are mutually fused and adhered under heating. Thestructure of the polymer particles (Y) can be selected appropriately inaccordance with the desired performance of the plastisol composition ofthe present invention and the articles formed therefrom, such as theimprovement of the dispersion stability of the polymer particles (Y)relative to plasticizers, or the prevention of stirring of powder.

[0033] For example, if the structure of the polymer particles (Y) is ahigher order structure with granulated secondary particles, thenstirring of powder of the polymer particles can be suppressed, thefluidity of the product plastisol composition can be improved, and thehandling and coating workability (hereinafter referred to workability)can be improved.

[0034] In the present invention, there are no particular restrictions onthe polymer particles (Y), and known polymer particles can be used.

[0035] Among known polymer particles, acrylic based polymer particlesare particularly preferable because they display good affinity with thecomponent (X), and the polymer particles (Y) can be readily plasticizedby heating. Furthermore, gelled films produced from plastisolcompositions using acrylic based polymer particles as the polymerparticles (Y) provide a markedly superior effect that plasticizer isprevented from bleeding out, and more stable than gelled films formedfrom conventional plastisols. As a result, when a plastisol compositionusing acrylic based polymer particles of the present invention is used,a gelled film with extremely good mechanical characteristics can beformed.

[0036] In those cases in which acrylic based polymer particles are usedas the polymer particles (Y), there are no particular restrictions onthe acrylic based polymer particles provided they are polymer particlesproduced by polymerization of an acrylic monomer.

[0037] The acrylic based polymer particles are preferably particlesformed from polymers (1) comprising, as structural components, methylmethacrylate units, methacrylate ester units (A1) which are esters of analcohol having 2 to 8 carbon atoms and methacrylic acid, and/or acrylateester units (A2) which are esters of an alcohol having 1 to 8 carbonatoms and acrylic acid, or polymers (2) comprising, as structuralcomponents, methyl methacrylate units, and monomer units (B) having ahigh polarity functional group of at least one selected from the groupconsisting of carboxyl groups, hydroxyl groups, sulfonic acid groups,phosphoric acid groups, and epoxy groups.

[0038] These acrylic based polymer particles display excellentcompatibility with the component (X), and are consequently preferred.

[0039] The methacrylate ester units (A1) and/or acrylate ester units(A2) which are components of the polymer (1) enable the compatiblitywith the component (X) to be controlled freely. Accordingly, when thepolymer (1) comprises these ester units (A1) and (A2), thickening can becontinuously suppressed, the dispersion stability of the polymerparticles can be improved, and the storage stability of the plastisolcomposition can be improved. This structure is preferable.

[0040] Furthermore, by using the components of the polymer (1), theglass transition temperature of the polymer particles can be adjusted asdesired, and the mechanical characteristics such as the hardness,strength, ductility, and the modulus of elasticity can be adjusted withease in accordance with the desired performance of the product article,which is preferable.

[0041] In the components of the polymer (1), specific examples of thecomponent (A1) and the component (A2) include (meth)acrylates ofstraight chain alkyl alcohols such as ethyl (meth)acrylate, n-butyl(meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, hexyl(meth)acrylate, 2-ethylhexyl (meth)acrylate, and octyl (meth)acrylate;or (meth)acrylates of cyclic alkyl alcohols such as cyclohexyl(meth)acrylate.

[0042] Among these, n-butyl (meth)acrylate, i-butyl (meth)acrylate,t-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate are preferred.These monomers are readily available which is an advantage from anindustrial viewpoint.

[0043] When the components of the polymer (2) are used, the affinitywith components (X) having particularly high polarity tends to be good,which is preferable. Furthermore, the gelled film obtained using theplastisol composition displays good dispersion medium retention and hasthe effect that plasticizer is prevented from bleeding out of thecomponent (X), which is also preferable.

[0044] In the components of the polymer (2), specific examples of themonomer unit (B) with a high polarity functional group include carboxylgroup containing monomers such as methacrylic acid, acrylic acid,itaconic acid, crotonic acid, maleic acid, fumaric acid,2-succinoyloxyethyl-2-methacryloyloxyethylsuccinic acid methacrylate,2-maleinoyloxyethyl-2-methacryloyloxyethylmaleic acid methacrylate,2-phthaloyloxyethyl-2-methacryloyloxyethylphthalic acid methacrylate,and 2-hexahydrophthaloyloxyethyl-2-methacryloyloxyethylhexahydrophthalicacid methacrylate; sulfonic acid group containing monomers such asallylsulfonic acid; hydroxyl group containing (meth)acrylates such as2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;phosphoric acid group containing (meth)acrylates such as2-(meth)acryloyloxyethyl acid phosphate; and epoxy group containing(meth)acrylates such as glycidyl (meth)acrylate. These monomers arereadily available which is an advantage from an industrial viewpoint.

[0045] The polymer (2) may also include monomer units (B2) other thanmethyl methacrylate units and the aforementioned monomer units (B) witha high polarity functional group. Specific examples of the monomer (B2)include carbonyl group containing (meth)acrylates such asacetoacetoxyethyl (meth)acrylate; amino group containing (meth)acrylatessuch as N-dimethylaminoethyl (meth)acrylate and N-diethylaminoethyl(meth)acrylate; polyfunctional (meth)acrylates such as (poly)ethyleneglycol di(meth)acrylate, propylene glycol di(meth)acrylate,1,6-hexanediol di(meth)acrylate, and trimethylolpropanetri(meth)acrylate; acrylamides and derivatives thereof such as diacetoneacrylamide, N-methylol acrylamide, N-methoxymethyl acrylamide,N-ethoxymethyl acrylamide, and N-butoxymethyl acrylamide; as well asstyrene and derivatives thereof, vinyl acetate, urethane modifiedacrylates, epoxy modified acrylates, and silicone modified acrylates.

[0046] The components of these polymer particles (Y) and the ratiothereof can be selected appropriately in accordance with the desiredperformance and intended uses of the articles produced from theplastisol composition of the present invention.

[0047] For example, from the viewpoint of improving the storagestability of the plastisol composition and the plasticizer retentioncharacteristics of the gelled film, when the polymer (1) is used, themass ratio between the methyl methacrylate units, and the methacrylateester units (A1) and/or the acrylate ester units (A2) is preferablywithin a range from 100/0 to 20/80, and even more preferably within arange from 100/0 to 40/60.

[0048] Furthermore, from the viewpoint of ensuring polymerizationstability in an emulsion polymerization, when the polymer (2) is used,the mass ratio between the methyl methacrylate units and the monomerunits (B) is preferably within a range from 100/0 to 50/50, and evenmore preferably within a range from 100/0 to 70/30.

[0049] In addition, in those cases in which the polymer particles (Y)are core/shell structures, the polymer comprising the core section andthe polymer comprising the shell section can each use a monomer producedby appropriate selection of the components from the aforementionedpolymers (1) or the aforementioned polymers (2).

[0050] A plastisol composition of the present invention comprisespolymer particles (Y) as described above dispersed within a polyalkyleneglycol and/or polyalkylene glycol derivative (X) as described above.

[0051] In the present invention, there are no particular restrictions onthe mass ratio between the component (X) and the component (Y), althoughratios within a range from 30/70 to 70/30 are preferred. If theproportion of the component (X) is less than a mass ratio of 30 (and themass ratio of the component (Y) exceeds 70), then the viscosity of thesol increases and the workability tends to deteriorate, whereas if theproportion of the component (X) is greater than a mass ratio of 70 (andthe mass ratio of the component (Y) is less than 30), then thedispersion medium within the plastisol composition tends to bleed outfrom the gelled film.

[0052] Furthermore, there are no particular restrictions on thecombination of the component (X) and the component (Y), although basedon the relationship between the component (X) and the solubilityparameter (hereafter abbreviated as the Sp value) of the polymerparticles (Y), the combination described below is preferable in terms ofgenerating superior storage stability of the composition. What is termedhere as the Sp value of the polymer particles (Y) refers to the Sp valueof the polymer which forms the entire particle when polymer particles(Y) form a uniform structure, or the Sp value of the polymer which formsthe shell when polymer particles (Y) form a core/shell structure. Spvalues in the present invention are determined by calculations using theknown Fedors method, and are reported in units of (J/cm³)^(1/2).

[0053] For example, in the case in which polyethylene glycol is used asthe component (X), polymer particles (Y) having an Sp value of 20.5 orless are preferred.

[0054] Furthermore, in the case in which polypropylene glycol is used asthe component (X), polymer particles (Y) having an Sp value within arange from 19.8 to 20.5 are preferred.

[0055] Furthermore, in the case in which polybutylene glycol is used asthe component (X), polymer particles (Y) having an Sp value of 19.6 ormore are preferred.

[0056] In addition, in cases in which the component (X) contains ahydroxyl group, an additional compound (Z) having a functional groupwhich reacts with the hydroxyl group of the component (X) may also beadded to a plastisol composition of the present invention. If thecompound (Z) with a functional group which can be chemically bonded withthe hydroxyl group of the component (X) is also added to the plastisolcomposition, then, the compound and the terminal hydroxyl group of thecomponent (X) are chemically bonded during film formation under heating,enabling the dispersion medium retention characteristics of the producedgelled film to be improved even further. This component (Z) can be addedto the dispersion medium.

[0057] Specific examples of the compound (Z) include isocyanates, epoxycompounds, organic acids, and acid anhydrides. These compounds may beused singularly, or in combinations of two or more compounds. Amongthese, compounds with an isocyanate group are preferred, and from theviewpoint of ensuring good storage stability of the product plastisolcomposition, blocked isocyanates in which the isocyanate group isprotected with a blocking agent, and acid anhydrides are particularlypreferred.

[0058] In those cases in which a component (Z) is used, the requiredquantity of the component (Z) can be added to the component (X) toprepare the plastisol composition.

[0059] Furthermore, where necessary, reaction inhibitors, reactionaccelerators, or dissociation catalysts may also be added to a plastisolcomposition of the present invention to adjust the reaction rate of thecomponent (X) and the component (Z).

[0060] Furthermore, where necessary, a variety of other additives mayalso be added to a plastisol composition of the present invention.

[0061] Examples of these other additives include known plasticizers,fillers such as calcium carbonate, aluminum hydroxide, baryta, clay,colloidal silica, mica powder, quartz sand, diatomaceous earth, kaolin,talc, bentonite, glass powder, and aluminum oxide; pigments such astitanium oxide and carbon black; diluents such as mineral turpentine andmineral spirit; as well as antifoaming agents, mold prevention agents,deodorants, antibacterial agents, surfactants, lubricants, ultravioletabsorbers, fragrances, foaming agents, leveling agents, and adhesives.

[0062] However, in order to form a low environmental impact plastisolcomposition, phthalate ester based plasticizers should preferably not beincluded.

Gelled Film

[0063] In a gelled film of the present invention, when a vinyl chloridefilm of dimensions 50×50×0.07 (mm) is placed on the surface of a gelledfilm of dimensions 50×50×2 (mm), and the gelled film is then retainedfor 24 hours at 80° C. with a pressure of 200 Pa applied from the sideof the vinyl chloride film, the amount of bleed out of the dispersionmedium is 1% or less of the total amount of the dispersion medium.

[0064] A gelled film of the present invention, in which little amount ofdispersion medium bleeds out, can be produced by using, for example, theaforementioned plastisol composition of the present invention.

[0065] There are no particular restrictions on the method of forming agelled film of the present invention, and, for example, in those casesin which an aforementioned plastisol composition is used, a formationmethod such as that described below can be used.

Method of Forming a Gelled Film

[0066] A plastisol composition of the present invention comprising apolyalkylene glycol and/or polyalkylene glycol derivative (X), andpolymer particles (Y) is prepared. The plastisol composition is appliedto a substrate to form a film, and the film is then heated so as to begelled, yielding a gelled film.

[0067] As a substrate, known materials, including inorganic materialssuch as glass and metal, or organic materials can be used. Furthermore,there are no particular restrictions on the shape of the substrate,provided a gelled film of the desired shape can be produced.

[0068] The method of applying the composition to the substrate can beselected appropriately in accordance with a substrate which enablesformation of the desired shape. Specific examples of the applicationmethod include known method such as knife coater methods, comma coatermethods, gravure printing methods, roll coating methods, rotary silkprinting methods, reverse coater methods, spray coating methods, andscreen coating methods.

[0069] There are no particular restrictions on the gelling conditionsused for producing a gelled film of the present invention, and thetemperature and treatment time can be selected appropriately inaccordance with factors such as the combination of the component (X) andthe component (Y).

[0070] For example, in cases in which a plastisol composition of thepresent invention is used, by setting the temperature conditions withina range from 70° to 260° C., and the treatment time within a range from30 seconds to 90 minutes, a uniform gelled film can be formed. Inaddition, from the viewpoint of productivity, particularly, thetemperature is preferably within a range from 120° to 220° C., and thetime within a range from 30 seconds to 30 minutes.

Article

[0071] An article of the present invention is an article formed from theaforementioned gelled film of the present invention, or an article witha coating formed from a gelled film of the present invention.

[0072] Specific examples of the former, namely, articles formed from agelled film include film like articles such as wallpaper and coatingsfor vehicle interiors, as well as three dimensionally shaped articlessuch as general merchandise, toys, and artificial food samples.

[0073] Specific examples of the latter, namely, articles with a coatingformed from a gelled film include floorings, vehicle undercoats, vehiclebody sealers, metal plates or wires coated with gelled films, andarticles covered with electrically insulating gelled films.

EXAMPLES

[0074] The present invention is explained more detail with reference toexamples.

[0075] The evaluation methods used in the examples are described below.

[0076] In the examples of the present invention, the workability of aplastisol composition was evaluated on the basis of storage stability.Furthermore, the processability of a gelled film was evaluated on thebasis of the strength of the gelled film and the quantity of dispersionmedium bleed out from the gelled film.

Weight Average Molecular Weight of Polymer Particles

[0077] Using the measurement conditions listed below, values(polystyrene equivalent values) measured using GPC methods were recordedas the weight average molecular weight.

[0078] Apparatus: High speed GPC Apparatus HLC-8020, manufactured byTOSOH CORPORATION

[0079] Column: Three TSKgelGMH_(XL) columns linked in series,manufactured by TOSOH CORPORATION

[0080] Oven temperature: 38° C.

[0081] Eluting solvent: tetrahydrofuran

[0082] Sample concentration: 0.4 mass %

[0083] Flow rate: 1 mL/minute

[0084] Injection quantity: 0.1 mL

[0085] Detector: RI (differential refractometer)

Storage Stability of Plastisol Composition

[0086] A produced plastisol composition was held at 25° C. in a constanttemperature water bath, and the initial viscosity was measured using aBM type viscometer (No. 4 rotor, manufactured by Toki Sangyo Co., Ltd.)with a speed of rotation of 6 rpm.

[0087] Subsequently, the plastisol composition was held at 30° C. in athermostatic chamber, and after 1 week the composition was removed andthe viscosity was measured using the same measurement conditions as theinitial viscosity measurement.

[0088] Next, the thickening efficiency of the plastisol compositionrelative to the initial viscosity was determined using the followingformula.

Thickening Efficiency (%)={(Viscosity following storage/initialviscosity)−1}×100

[0089] Based on this thickening efficiency, the storage stability wasevaluated using the following evaluation standards.

[0090] ⊚: less than 40%

[0091] ◯: 40% or more and less than 60%

[0092] Δ: 60% or more and less than 100%

[0093] ×: 100% or more

Strength of Gelled Film

[0094] A produced gelled film was peeled away from the substrate, cutinto a dumbbell No. 3 shape to prepare a test piece. The strength of thetest piece was then measured using a tensile tester. The measurementconditions included a test speed of 200 mm/min., a load cell rating of980 N, and a surrounding temperature of 25° C.

[0095] The measured strength values were evaluated on the basis of thefollowing evaluation standards.

[0096] ⊚: 3.0 MPa or more

[0097] ◯: 2.0 MPa or more and less than 3.0 MPa

[0098] Δ: 1.0 MPa or more and less than 2.0 MPa

[0099] ×: less than 1.0 MPa

Dispersion Medium Bleed Out from Gelled Film

[0100] A vinyl chloride film of dimensions 50×50×0.07 (mm) was placed onthe surface of a produced gelled film (50×50×2 (mm)), and the gelledfilm was then retained for 24 hours in a thermostatic chamber at 80° C.with a pressure of 200 Pa applied from the side of the vinyl chloridefilm.

[0101] The amount of dispersion medium bleed out from the gelled filmwas determined from the variation in the mass of the film across theduration of the test, using the following formula.

Amount of bleed out of dispersion medium (mg)=(film mass aftertesting)−(initial film mass)

[0102] The amount of bleed out of dispersion medium was then evaluatedon the basis of the following evaluation standards.

[0103] ⊚: less than 5 mg

[0104] ◯: 5 mg or more and less than 10 mg

[0105] Δ: 10 mg or more and less than 30 mg

[0106] ×: 30 mg or more

Preparation of Polymer Particles (A1)

[0107] 500 g of pure water was placed in a 2 liter 4 neck flask equippedwith a thermometer, a nitrogen gas inlet tube, a stirrer, a droppingfunnel, and a cooling pipe, and nitrogen gas was bubbled through thewater for 30 minutes to remove any residual dissolved oxygen from thepure water.

[0108] Subsequently, the nitrogen bubbling was changed to a nitrogenflow, and 16.3 g of methyl methacrylate and 12.5 g of n-butylmethacrylate were added, and with the mixture being stirred at 200 rpm,the temperature was raised to 80° C. When the internal temperature hadreached 80° C., 0.25 g of potassium persulfate dissolved in 10 g of purewater was added to the flask in a single batch to initiate thepolymerization. Subsequently, stirring was continued at 80° C. for 60minutes, yielding a seed particle dispersion. This polymerization is asoap-free polymerization that uses no emulsifiers.

[0109] Subsequently, a monomer emulsion produced by mixing, stirring,and emulsifying 128.5 g of methyl methacrylate, 121.5 g of n-butylmethacrylate, 2.50 g of sodium dioctylsulfosuccinate and 125.0 g of purewater was added dropwise to the seed particle dispersion over 2 hours.Stirring was then continued for a further 1 hour at 80° C., yielding apolymer dispersion of core particles.

[0110] Subsequently, a monomer emulsion produced by mixing, stirring,and emulsifying 250.0 g of methyl methacrylate, 2.50 g of sodiumdioctylsulfosuccinate, and 125.0 g of pure water was added dropwise tothe polymer dispersion of core particles over 2 hours. Stirring was thencontinued for a further 1 hour at 80° C., yielding a core/shell typepolymer dispersion.

[0111] The core/shell type polymer dispersion was cooled to roomtemperature, and then spray dried using a spray dryer, yielding polymerparticles (A1).

[0112] The drying conditions for the spray drying included an inlettemperature of 170° C., an outlet temperature of 75° C., and an atomizerrotational speed of 25,000 rpm.

[0113] The thus produced polymer particles (A1) had a volume averageparticle size of 0.79 μm, and a weight average molecular weight of862,000 of primary particles.

Preparation of Polymer Particles (A2) to (A4)

[0114] With the exceptions of altering the monomers of the monomeremulsion which is added dropwise to the compositions shown in Table 1,and altering the quantity of the core to 250 g, and that of the shell to250 g, polymer particles (A2) to (A4) were prepared using the samemethod as that used for the polymer particles (A1).

Preparation of Polymer Particles (A5)

[0115] 500 g of pure water was placed in a 2 liter 4 neck flask equippedwith a thermometer, a nitrogen gas inlet tube, a stirrer, a droppingfunnel, and a cooling pipe, and nitrogen gas was bubbled through thewater for 30 minutes to remove any residual dissolved oxygen from thepure water.

[0116] Subsequently, the nitrogen bubbling was changed to a nitrogenflow, and 16.3 g of methyl methacrylate and 12.5 g of n-butylmethacrylate were added, and with the mixture being stirred at 200 rpm,the temperature was raised to 80° C. When the internal temperature hadreached 80° C., 0.25 g of potassium persulfate dissolved in 10 g of purewater was added to the flask in a single batch to initiate thepolymerization. Subsequently, stirring was continued at 80° C. for 60minutes, yielding a seed particle dispersion. This polymerization is asoap-free polymerization that uses no emulsifiers.

[0117] Subsequently, a monomer emulsion produced by mixing, stirring andemulsifying 431.9 g of methyl methacrylate, 68.1 g of t-butylmethacrylate, 5.0 g of sodium dioctylsulfosuccinate, and 250.0 g of purewater was added dropwise to the seed particle dispersion over 5 hours.Stirring was then continued for a further 1 hour at 80° C., yielding apolymer dispersion.

[0118] This polymer dispersion was cooled to room temperature, and thenspray dried using a spray dryer, yielding polymer particles (A5).

[0119] The thus produced polymer particles (A5) had a volume averageparticle size of 0.82 μm, and a weight average molecular weight of815,000 of primary particles. TABLE 1 Core Shell Primary Weight averagePolymer Core composition Sp Shell composition Sp particle size molecularparticles (mol ratio) value (mol ratio) value (μm) weight A1 MMA/n-BMA =60/40 19.74 MMA = 100 20.15 0.79 862,000 A2 MMA/n-BMA = 60/40 19.74MMA/GMA = 80/20 20.27 0.66 802,000 A3 MMA/MAA = 80/20 20.81 MMA/MAA =95/5 20.31 0.74 940,000 A4 MMA/n-BMA = 60/40 19.74 MMA/n-BMA = 90/1020.05 0.87 764,000 A5 MMA/t-BMA = 90/10 19.97 — — 0.82 815,000

Example 1

[0120] To 100 parts by mass of the polymer particles (A1) was added 100parts by mass of a polypropylene glycol with a weight average molecularweight of 700 (an average degree of polymerization of 12) (brand name:ADEKA POLYETHER P-700, manufactured by Asahi Denka Co., Ltd.) as adispersion medium. This mixture was then mixed and stirred using adisper mixer, and then defoamed under reduced pressure, yielding aplastisol composition with the polymer particles dispersed uniformly.The initial viscosity of this plastisol composition was 1.5 Pa•s and thethickening efficiency was 52%, indicating good storage stability.

[0121] Furthermore, the thus obtained plastisol composition was appliedto a glass plate to form a film of thickness 2 mm, and was then heatedfor 30 minutes at 140° C., yielding a gelled film.

[0122] This gelled film displayed very good film coatingcharacteristics, with a strength of 2.8 MPa and the amount of bleed outof a dispersion medium of 0.0 mg.

Example 2

[0123] With the exception of using a polypropylene glycol with a weightaverage molecular weight of 2000 (an average degree of polymerization of35) (brand name: Adeka polyether P-2000, manufactured by Asahi DenkaCo., Ltd.) as the dispersion medium, a plastisol composition containinga uniform dispersion of polymer particles was prepared, and a gelledfilm was formed, using the same method as the example 1.

Example 3

[0124] With the exception of using (A2) for the polymer particles, aplastisol composition containing a uniform dispersion of polymerparticles was prepared, and a gelled film was formed, using the samemethod as the example 1.

Example 4

[0125] With the exceptions of using (A3) for the polymer particles, andusing a polyethylene glycol with a weight average molecular weight of400 (an average degree of polymerization of 9.1) (brand name:polyethylene glycol 400, manufactured by Katayama Chemical Inc.) as thedispersion medium, a plastisol composition containing a uniformdispersion of polymer particles was prepared, and a gelled film wasformed, using the same method as the example 1.

Example 5

[0126] With the exceptions of using (A4) for the polymer particles, andusing a polybutylene glycol with a weight average molecular weight of650 (an average degree of polymerization of 9.0) (brand name: PTG-650SN,manufactured by Hodogaya Chemical Inc.) as the dispersion medium, aplastisol composition containing a uniform dispersion of polymerparticles was prepared, and a gelled film was formed, using the samemethod as the example 1.

Example 6

[0127] With the exception of adding 23.7 parts by mass of a blockedisocyanate containing tetramethylxylene diisocyanate (brand name:m-TMXDI, manufactured by Takeda Chemical Industries Ltd.) blocked withmethyl ethyl ketoxime as a component (Z), a plastisol compositioncontaining a uniform dispersion of polymer particles was prepared, and agelled film was formed, in the same manner as the example 1.

Example 7

[0128] With the exception of adding 14.6 parts by mass of3,5,5-trimethylhexanoic acid (brand name: Kyowanoic N, manufactured byKyowa Hakko Kogyo Co., Ltd.), and 1.0 parts by mass of1,2-dimethylimidazole as a component (Z), a plastisol compositioncontaining a uniform dispersion of polymer particles was prepared, and agelled film was formed, in the same manner as the example 1.

Example 8

[0129] With the exception of using the polymer particles (A5) instead ofthe polymer particles (A1), a plastisol composition containing a uniformdispersion of polymer particles was prepared and a gelled film wasformed, in the same manner as the example 1.

Example 9

[0130] To 100 parts by mass of the polymer particles (A2) was added 100parts by mass of a polypropylene glycol with a weight average molecularweight of 2000 (an average degree of polymerization of 34) as adispersion medium, and 7.7 parts by mass of hexahydrophthalic anhydride(brand name: Rikacid HH, manufactured by New Japan Chemical Co., Ltd.)as a component (Z). This mixture was then mixed and stirred using adisper mixer, and then defoamed under reduced pressure, yielding aplastisol composition with the polymer particles dispersed uniformly.The initial viscosity of this plastisol composition was 9.5 Pa•s and thethickening efficiency was 39%, indicating good storage stability.

[0131] Furthermore, the obtained plastisol composition was used to forma gelled film in the same manner as the example 1.

Comparative Example 1

[0132] With the exception of adding 100 parts by mass ofdiisononylphthalic acid (DINP) as a dispersion medium to 100 parts bymass of vinyl chloride polymer particles (brand name: Zeon 121,manufactured by Zeon Corporation), a plastisol composition was prepared,and a gelled film was formed, using the same method as the example 1.

Comparative Example 2

[0133] With the exception of adding 100 parts by mass ofdiisononylphthalic acid (DINP) as a dispersion medium to 100 parts bymass of the produced polymer particles (A4), a plastisol composition wasprepared, and a gelled film was formed, using the same method as theexample 1.

Comparative Example 3

[0134] With the exception of adding 100 parts by mass of tricresylphosphate (TCP) as a dispersion medium to 100 parts by mass of theproduced polymer particles (A4), a plastisol composition was prepared,and a gelled film was formed, using the same method as the example 1.

Comparative Example 4

[0135] With the exception of adding 50 parts by mass of dipropyleneglycol dibenzoate (DPG-BZ) and triethylene glycol bis-2-ethylbutyrate(TEG-2EB) as a dispersion medium to 100 parts by mass of the producedpolymer particles (A1), a plastisol composition was prepared, and agelled film was formed, using the same method as the example 1.

Comparative Example 5

[0136] With the exception of adding 100 parts by mass of diethyleneglycol dibenzoate (DEGB) as a dispersion medium to 100 parts by mass ofthe produced polymer particles (A1), a plastisol composition wasprepared using the same method as the example 1. The obtained plastisolcomposition gelled during the storage stability test and displayed poorstorage stability.

[0137] The results of the evaluations of the examples 1 to 5 are shownin Table 2. The results of the evaluations of the examples 6 to 9 areshown in Table 3. The results of the evaluations of the comparativeexamples 1 to 5 are shown in Table 4. TABLE 2 Exam- Exam- Exam- Exam-Exam- ple 1 ple 2 ple 3 ple 4 ple 5 Dispersion medium (X) P700 P2000P700 PEG PBG Polymer particles (Y) A1 A1 A2 A3 A4 Compound (Z) — — — — —Initial viscosity (Pa · s) 1.5 10.1 1.2 2.5 2.0 Thickening efficiency 5217 33 45 54 (%) Storage stability ◯ ⊚ ⊚ ◯ ◯ Strength (MPa) 2.8:◯ 4.1:⊚3.2:⊚ 3.5:⊚ 2.4:◯ Amount of bleed out of 0.0:⊚ 0.0:⊚ 0.0:⊚ 0.0:⊚ 3.0:⊚dispersion medium (mg)

[0138] TABLE 3 Example 6 Example 7 Example 8 Example 9 Dispersion medium(X) P700 P700 P700 P2000 Polymer particles (Y) A1 A2 A5 A2 Compound (Z)BI DMI — HHF Initial viscosity (Pa · s) 8.2 4.9 2.4 9.5 Thickeningefficiency 42 27 22 39 (%) Storage stability ◯ ⊚ ⊚ ⊚ Strength (MPa)4.5:⊚ 1.8:Δ 2.3:◯ 5.2:⊚ Amount of bleed out of 0.0:⊚ 0.0:⊚ 0.0:⊚ 0.0:⊚dispersion medium (mg)

[0139] Abbreviations within the Table 2 and the Table 3 are as follows:

[0140] P700: polypropylene glycol (weight average molecular weight 700,average degree of polymerization 12)

[0141] P2000: polypropylene glycol (weight average molecular weight2000, average degree of polymerization 34-35)

[0142] PEG: polyethylene glycol (weight average molecular weight 400,average degree of polymerization 9.1)

[0143] PBG: polybutylene glycol (weight average molecular weight 650,average degree of polymerization 9.0)

[0144] BI: blocked isocyanate containing tetramethylxylene diisocyanateblocked with methyl ethyl ketoxime

[0145] TMH: 3,5,5-trimethylhexanoic acid

[0146] DMI: 1,2-dimethylimidazaole

[0147] HHF: hexahydrophthalic anhydride TABLE 4 Comparative ComparativeComparative Comparative Comparative Example 1 Example 2 Example 3Example 4 Example 5 Dispersion medium (X) DINP DINP TCP DPG-BZ/ DEGBTEG-2EB Polymer particles (Y) PVC A4 A4 A1 A1 Compound (Z) — — — — —Initial viscosity (Pa · s) 0.8 1.8 2.7 3.1 1.5 Thickening efficiency (%)42 28 58 18 gelled Storage stability ◯ ⊚ ◯ ⊚ X Strength (MPa) 3.8:⊚3.2:⊚ 3.2:⊚ 3.5:⊚ 0.9:X Amount of Bleed out 28.4:Δ 38.6:X 32.5:X 30.5:X7.6:◯ dispersion medium (mg)

[0148] Abbreviations within the Table 4 are as follows:

[0149] PVC: polyvinyl chloride polymer particles

[0150] DINP: diisononylphthalic acid

[0151] TCP: tricresyl phosphate

[0152] DPG-BZ: dipropylene glycol dibenzoate

[0153] TEG-2EB: triethylene glycol bis-2-ethylbutyrate

[0154] DEGB: diethylene glycol dibenzoate

Observations from Each of the Examples and the Comparative Examples

[0155] Examples 1 to 5

[0156] The examples 1 to 3 are examples which used polypropylene glycolas the dispersion medium, whereas the example 4 used polyethylene glycolas the dispersion medium, and the example 5 used polybutylene glycol asthe dispersion medium.

[0157] Each of the plastisol compositions prepared in the examples 1 to5 displayed good storage stability and good workability.

[0158] Furthermore, the gelled films obtained by applying and heatingthe plastisol compositions displayed good strength, and almost no bleedout of the dispersion medium.

[0159] Examples 6 and 7

[0160] The examples 6 and 7 are examples of plastisol compositionscontaining a compound which reacts with the hydroxyl groups of thepolypropylene glycol. These plastisol compositions displayed even betterstorage stability than the example 1, which contained no such addedcompound, and the workability was also good.

[0161] The gelled films obtained by applying and heating these plastisolcompositions contained almost no residual low molecular weight fraction,displayed absolutely no bleed out of the dispersion medium, and alsoprovided good strength.

[0162] Example 8

[0163] The example 8 is an example of a plastisol composition which useda copolymer of methyl methacrylate and t-butyl methacrylate as thepolymer particles, and polypropylene glycol as the dispersion medium.These polymer particles did not display compatiblity with polypropyleneglycol, and consequently the plastisol composition had extremely goodstorage stability, as well as good workability.

[0164] When this plastisol composition was applied and heated,elimination of isobutylene causes a conversion to a compatible resin,and consequently the produced gelled film displayed completely no bleedout of the dispersion medium, and also provided good strength.

[0165] Example 9

[0166] The example 9 is an example of a plastisol composition containingan added acid anhydride which reacts with the hydroxyl groups of thepolypropylene glycol. The plastisol composition had extremely goodstorage stability, as well as good workability.

[0167] The gelled film obtained by applying and heating this plastisolcomposition displayed completely no bleed out of the dispersion medium,and also provided good strength.

Comparative Example 1

[0168] The comparative example 1 is a plastisol composition which usedpolyvinyl chloride polymer particles, and a phthalic acid basedplasticizer as the dispersion medium. This plastisol compositiondisplayed good storage stability and good workability. However, becausethe composition uses halogen atom containing polymer particles, itsuffers from an environmental problem in that it emits materials such asdioxin on incineration.

[0169] Furthermore, the gelled film obtained by applying and heatingthis plastisol composition displayed a large amount of bleed out of thedispersion medium, and a good gelled film was not obtained.

Comparative Example 2

[0170] The comparative example 2 is a plastisol composition which usedacrylic based polymer particles, and a phthalic acid based plasticizeras the dispersion medium. This plastisol composition displayed goodstorage stability and good workability.

[0171] However, the gelled film obtained by applying and heating thisplastisol composition displayed a large amount of bleed out of thedispersion medium, and a good gelled film was not obtained.

Comparative Example 3

[0172] The comparative example 3 is a plastisol composition which usedacrylic based polymer particles, and a phosphoric acid based plasticizeras the dispersion medium. This plastisol composition displayed goodstorage stability and good workability.

[0173] However, the gelled film obtained by applying and heating thisplastisol composition displayed a large amount of bleed out of thedispersion medium, and a good gelled film was not obtained.

Comparative Example 4

[0174] The comparative example 4 is a plastisol composition which usedacrylic based polymer particles, and a combination of an ether esterbased plasticizer and a benzoate ester plasticizer as the dispersionmedium. This plastisol composition displayed good storage stability andgood workability.

[0175] However, the gelled film obtained by applying and heating thisplastisol composition displayed a large amount of bleed out of thedispersion medium, and a good gelled film was not obtained.

Comparative Example 5

[0176] The comparative example 5 is a plastisol composition which usedacrylic based polymer particles, and diethylene glycol dibenzoate as thedispersion medium. This plastisol composition displayed no good storagestability and workability.

[0177] Furthermore, the gelled film obtained by applying and heatingthis plastisol composition also displayed no good strength.

INDUSTRIAL APPLICABILITY

[0178] A plastisol composition of the present invention uses non-halogenbased polymer particles with no halogen atoms, which do not emitmaterials such as hydrogen chloride gas or dioxin on incineration, anddoes not require a phthalic acid based plasticizer as a dispersionmedium, and consequently provides an extremely large reduction inenvironmental impact. Furthermore, by using the plastisol composition, agelled film having no bleed out of the dispersion medium, superiordispersion medium retention characteristics, workability, andprocessability is obtained. In addition, by using the plastisolcomposition of the present invention, a gelled film or an article withexcellent mechanical characteristics are provided.

[0179] The present invention can also be implemented in a variety ofother modified forms, provided such modifications do not deviate fromthe burden of the invention. The examples described above merelyrepresent a series of different examples, and must not be interpreted aslimiting in any way. Furthermore, the scope of the present invention isdefined by the scope of the claims, and is in no way restricted by themain body of text of this description. In addition, modifications andvariations which fall within an equivalent scope to that of the presentinvention are all deemed as falling within the scope of the presentinvention.

1. A plastisol composition comprising a polyalkylene glycol and/or apolyalkylene glycol derivative (X), and polymer particles (Y).
 2. Aplastisol composition according to claim 1, wherein said polyalkyleneglycol and/or polyalkylene glycol derivative (X) is represented by ageneral formula (1) shown below:

(wherein, R₁ and R₂ each represent a hydrogen atom or an alkyl grouphaving 1 to 10 carbon atoms, R₃ represents a straight chain or branchedalkylene group having 2 to 12 carbon atoms, and n which represents aninteger within a range from 5 to 200).
 3. A plastisol compositionaccording to claim 1, wherein said polyalkylene glycol and/orpolyalkylene glycol derivative (X) is at least one compound selectedfrom the group consisting of polyethylene glycol, polypropylene glycol,and polybutylene glycol.
 4. A plastisol composition according to claim1, wherein said polymer particles (Y) are particles with a core/shellstructure or a gradient structure.
 5. A plastisol composition accordingto claim 1, wherein said polymer particles (Y) have primary particleswith a volume average particle size for primary particles of 0.01 to50.0 μm.
 6. A plastisol composition according to claim 1, wherein saidpolymer particles (Y) are powder formed by spray drying.
 7. A plastisolcomposition according to claim 1, wherein said polymer particles (Y) areacrylic based polymer particles.
 8. A plastisol composition according toclaim 1, wherein said polyalkylene glycol and/or polyalkylene glycolderivative (X) is polyethylene glycol, and said polymer particles (Y)have a solubility parameter of 20.5 or less.
 9. A plastisol compositionaccording to claim 1, wherein said polyalkylene glycol and/orpolyalkylene glycol derivative (X) is polypropylene glycol, and saidpolymer particles (Y) have a solubility parameter within a range from19.8 to 20.5.
 10. A plastisol composition according to claim 1, whereinsaid polyalkylene glycol and/or polyalkylene glycol derivative (X) ispolybutylene glycol, and said polymer particles (Y) have a solubilityparameter of 19.6 or more.
 11. A plastisol composition according toclaim 1, wherein said polymer particles (Y) comprise, as components,methyl methacrylate units, and methacrylate ester units (A1) which areesters of an alcohol having 2 to 8 carbon atoms and methacrylic acid,and/or acrylate ester units (A2) which are esters of an alcohol having 1to 8 carbon atoms and acrylic acid.
 12. A plastisol compositionaccording to claim 1, wherein said polymer particles (Y) comprise, ascomponents, methyl methacrylate units, and monomer units (B) whichcomprise at least one type of high polarity functional group selectedfrom the group consisting of carboxyl groups, hydroxyl groups, sulfonicacid groups, phosphoric acid groups, and epoxy groups.
 13. A plastisolcomposition according to claim 1, wherein said polyalkylene glycoland/or polyalkylene glycol derivative (X) contains a hydroxyl group, andsaid plastisol composition further comprises a compound (Z) having afunctional group which reacts with said hydroxyl group.
 14. A gelledfilm comprising a dispersion medium, in which an amount of bleed out ofsaid dispersion medium is 1% or less of a total amount of the dispersionmedium when a vinyl chloride film of dimensions 50×50×0.07 (mm) isplaced on a surface of a gelled film of dimensions 50×50×2 (mm), andsaid gelled film is then retained for 24 hours at 80° C. with a pressureof 200 Pa applied from a side of said vinyl chloride film.
 15. A gelledfilm according to claim 14, which is a film produced by gelling aplastisol composition according to claim
 1. 16. A gelled film accordingto claim 14, which is other than phthalate ester based plasticizers. 17.An article comprising a gelled film according to claim
 14. 18. Anarticle comprising a coating which comprises a gelled film according toclaim 14.